Photographic color-forming compounds



- Patented s. 26, 1938.

PATENT OFFICE 2,115,394 rno'roonsrmc COLOB-FORLHNG comromms Leopold n. Mannes, Leopold Godowsky, Jr., and Willard D. Peterson; Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. -Y.',

.a corporationof New Jersey No Drawing. Application October 14, 1936, Serial him-105,617 p '12 Claims. (o1, 95-'-88) invention'relates photographic developers and more particularlytocompounds which Marines and L. Godowsky, Jr.

We have found that certain organic compounds containing the cyanoacetyl group as a substituent are useful as coupler compounds in photoform dyes by coupling withthe developing com-' pound on development.

The methodof forming colored photographic images by depositinga colored compound in the photographic. layer adjacent the silver image on development has been described in numerous prior patents. The present invention relates to a process in which the color-forming compound is contained preferably in the developing solution, but might also be incorporated in the sensitive materialand forms a dye simultaneously and in situ' with the development of the silver image bycoupling with the oxidation product of; the photo-- graphic developer In U. S. Patent No. 2,039,730, granted May 5, 1936,- to L.*".D. Marines and L;

Godowsky, Jr; there is disclosed theuseof hy- .droxylat'ed diphenyl compounds for this purpose. The use of other types of compounds was also described in application, Serial graphic developers and form colored images on photographic development; j The compounds which we contemplate using have the following.

general formula; 2

in which R may be one of the following groups: acenaphthe'nyl', 'dibenzofuryl, coumaronyl or phenoxyphe'nyl. The compounds containing-these 0 groups attached to a cyanoacetyl group will have the following formulae:

. tylaeenaphthene eo-cm-cN These compounds when present in a developer No. 8519, of L. D.

uct of the'aromatic amino developingcompound form a dye simultaneously with the formation of the silver image. The coupling occurs in each case'at the methylene group contained between the carbonyl group'and' the cyano group of the coupler compound; p

Thecouplercompounds used may be substi-.' tuted in the aromatic-ring with groups-including halide,- nitro,. amino, substituted amino, alkyl, aryl and carboxyl groups. These groups may be substituted in the ring-at any .position since the ring is not reactive in" the coupling to form the dy 'As' developing agents we contemplate using the aromatic aminocompounds' which function as photographic developers. .The compounds preferred for this "purpose are para phenylenediamine and its substituted derivatives. These developers may be substituted in 'thetaminogroups as well as in theririg with alkyl, ester, or halide 'or sulfatesince these compounds are more stable than the amines themselves-.2 Developing agents which may-be used include diethyl para phenylenedia'mine, monomethyl para phenylenediamine hydrochloride and diethylene p'ara phen- Yknediamine sulfate. A developing formula which may be used is the tone, such as 'alcohols. may also be used.

- The colors formed 'bythe compounds of the present invention on coupling with the oxidlzatlon 'product of. the developer are various shades of red andmagenta. 'The colors may,. of course, be

" altered by inserting various substituent groups into themolecule of the coupler compounds.

followingrq' A I j Diethyl para phenylenediaminehydrochlo .rlde 3 am" 1 Sodium sulflteln do '0. 5

Sodiuin carbonate grams 20 .Water I V lifre' 1 B Coupler gram 1 Acetone I on -50 AddBtoA'; a

Although we have described our invention with particular reference to the use of the coupling compound in the developing solution itself, our invention is in no way limited to this method.

As, an alternative method, the coupler compound may be incorporated in the photographic-layer before development, or before exposure and dephotographic images in films plates, or paper, when gelatin or other suitable colloid is .used as 'velopment. It maybe adsorbed to the sensitive silver halide grain or chemically combined with I 10 the sensitive salt, or, in some cases, the silver 'salt of the coupler compound itself, without halide, may exhibit light sensitivity and coupling :properties on development. l

Our compounds may be used to form colored the carrier for the silver halide constituting the sensitive salt. The emulsion treated to form the I colored image may be on one side or on both sides of the support or superposed emulsion layers may be coated on one or both sides of the support. Where a plurality of layers is used the layers may be difierently sensitized to form natural colored images on development, according to the process described inapplication, Serial No. 8,516, filed February 27, 1935, 'by L. D. Mannes and L. Godowsky, Jr.

What we claim is: I

1. A color-forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and a coupler compound having the formula drochloride' and a coupler compound having the I I formula I q where R is selected from the class consisting of acenaphthenyl, dibenzofuryl, coumaronyl, and phenoxyphenyl groups.

4. A color-forming" photographic developer I an aromatic amino developing compoundacontaining a primary amino group and 3-m cyanoacetyl-acenaphthene.

5. A color-forming photographic developer comprising comprising a dialkyl amino paraphenylene diamine developing compound and "'3- 'cyanoacetyl-acenaphthene.

' 6. A color-forming photographic developer comprising diethyl paraphenylene diamine hydrochloride and 3-w-cyanoacetyl-diphenyleneoxide.

7. A- color-forming photographic developer comprising :an aromatic amino developing compound containing a primary amino group and 1- (w-cyano'acetyl) -coumaro'ne.

acetyl) -coumarone.

9., A color-forming developer comprising diethyl para phenylenediaminehydrochloride and l- (w-cyanoacetyl) -coumarone.

10. A photographic image-comprising a dye .formed by the coupling of thedevelopment product of an aromatic amino developing compound containing a primary amino group with a compound having the formula r where R is selected from the class consisting of acenaphthenyl, dibenzofuryl, coumaronyl, and phenoxyphenyl groups.

11. A photographic image comprising a dye formed by the coupling of the development product of a dialkyl amino paraphenylene diamine with a compound having the formula R-CO-CHzi-CN where R is selected from'the class consisting of acenaphthenyl, dibenzofuryl, coumaronyl, and phenoxyphenyl groups. I 12. The method. of producing a colored photographic image in a gelatino-silv'er halide emulsion layer which comprises coupling the development product of an aromatic amino developing compound containing a primary amino group with a compound having the formulav I R-COCH2CN' I where R. is selected from the class consisting of acenaphthenyl, dibenzofuryl, coumaronyl, and

phenoxyphenyl groups. I I

LEOPOLD D. MANNES. moron) GODOWSKY, JR. WILLARDVD. PETERSON.

15 8. A eOlorforming photographic developer 7 comprising a dialkyl amino paraphenylene diamine developing compound and l-(w-cyano- 

